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Materials Science
Volume 6, Number 4
Combinatorial Materials Science for Energy Applications Lanthanide Ions as Photon Managers for Solar Cells
Introduction
Welcome to the fourth issue of Material Matters for 2011, focusing on Materials for Energy Efficiency: Thermoelectrics, Thin Films and Phosphors.
TM
Vol. 6, No. 4
Aldrich Materials Science Sigma-Aldrich Co. LLC 6000 N. Teutonia Ave. Milwaukee, WI 53209, USA
Introduction
Global energy demands are continuing to increase. To date, fossil fuels have served as a major energy source, to meet these ever growing energy needs. It is generally accepted that while fossil fuel technology is well developed, it is not sustainable and its subsequent carbon footprint is the contributing factor to global warming. Climate change, increasing energy demands and depletion of conventional Meenakshi Hardi, Ph.D. energy sources all indicate that alternative energy must play a bigger Aldrich Materials Science role in the future. Alternative energy sources are renewable, and Sigma-Aldrich Co. LLC environmentally clean. These include solar power, hydrogen energy, and biofuel as well as wind, hydroelectric and geothermal energy. In addition to developing alternative energy sources to meet growing energy requirements, it is equally important to improve the efficiency of energy generation. Energy efficiency and alternative energy are said to be the twin pillars of sustainable energy policy. Approximately 90% of the worlds electricity is generated by thermal energy, typically operating at only 3040% efficiency, losing a major portion of the energy in the form of radiant heat to the environment. Materials exhibiting the thermoelectric effect, a phenomenon in which a temperature difference creates an electric potential or vice versa, can convert some of this lost heat into useful electricity, thus increasing the overall efficiency of the energy generation. Thermoelectric materials have also been explored for other applications, for example, to capture heat lost in the exhaust of automobiles to produce electricity for the vehicle. An alternative way of generating electricity is by using solar cells, which converts the energy of light into electricity by photovoltaic effect. Solar energy is one of the most promising sustainable energy sources. Solar currently contributes less than 1% of the worlds energy supply. The relatively high cost per kilowatt-hour and the efficiency of commercial solar cells have limited their utility. The main loss of efficiency in the conversion of solar energy into electrical energy is due to spectral mismatch, wherein the low energy photons are not absorbed and high energy photons are not efficiently used by a solar cell. Spectral conversion by using materials, such as lanthanides with high luminescence efficiencies and rich energy level structure, can covert these high and low energy photons to desired wavelengths, thus significantly increasing the efficiency of solar cells. The focus of this issue of Material Matters is Materials for Energy Efficiency. The first two articles highlight novel thermoelectric materials, which are not based on widely used chalcogenides. In the first article, Prof. Anke Weidenkaff (EMPA-Swiss Federal Laboratories for Materials Science and Technology, Switzerland) describes the advantages of perovskitetype oxide materials, such as their flexibility and relatively simple and predictable structure property relationship, thus making them novel thermoelectric materials. In the second article, Prof. Mikhail Fedorov (Ioffe Physical-technical Institute, St. Petersburg, Russia) describes metal silicides as another class of promising thermoelectrics. Prof. Bruce van Dover from Cornell University, USA, reports an efficient way of screening materials for different energy-related applications using the Codeposited Composition Spread (CCS) techniquea variant of high-throughput synthesis methods. In the last article, Prof. Andries Meijerink from Utrecht University, Netherlands, explores the emerging concept of spectral conversion in the field of photovoltaics, by using lanthanide ions to increase the efficiency of solar cells. Each article in this publication is accompanied by a list of relevant materials available from Aldrich Materials Science. For additional product information, please visit Aldrich Materials Science at Aldrich.com/matsci. Please send us your comments or suggestions for Material Matters or your product suggestions at matsci@sial.com.
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Dr. Jacques Huot of Universit du Qubec Trois-Rivires kindly suggested that we offer high purity magnesium ingots (Aldrich Prod. No. 735779), suitable for the preparation of hydrogen storage metals. Recent studies have shown that cold-processing of bulk magnesium can drastically increase hydrogen sorption properties relative to untreated powdered magnesium.1 Magnesium is also used in the production of biodegradable implants (Mg-Mn-Zn),2 battery materials,3 light weight structural alloys (Mg-Al and Mg-Al-Zn),4-5 and corrosion resistance coatings for steel parts.6-7 Larger forms of elemental magnesium can be used in metallurgical processes and are beneficial due to a reduced amount of surface oxidation compared to magnesium powder or turnings.
References
1. 2. 3. 4. 5. 6. 7. Huot, J.; Balema, V. Material Matters 2010, 5, 112. Xu, L.; Pan, F.; Yu, G.; Yang, L.; Zhang, E.; Yang, K. Biomaterials 2009, 30, 1512. Pedneault, S.; Huot, J.; Roue, L. J. Power Sources 2008, 185, 566. Pardo, A.; Merino, M.C.; Coy, A.E.; Arrabal, R.; Viejo, F.; Matykina, E. Corros. Sci. 2008, 50, 823. Huang, X.; Suzuki, K.; Watazu, A.; Shigematsu, I.; Saito, N. J. Alloys Compd. 2008, 457, 408. Ambat, R.; Aung, N.N.; Zhou, W. Corros. Sci. 2000, 42, 1433. Jiang, Z.; Li, S.; Zeng, J.; Liao, X.; Yang, D. Adv. Mater. Res. 2011, 189-193, 1248.
12
Magnesium
Atomic Number: 12 Electronic Con guration: [Ne]3s2 Atomic Weight: 24.305
ingot
Table of Contents
Articles
Thermoelectric Performance of Perovskite-type Oxide Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 Silicides: Promising Thermoelectric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 Combinatorial Materials Science for Energy Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 Lanthanide Ions as Photon Managers for Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Featured Products
Materials for Perovskite Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 (A list of metal oxides, alkoxides, and salts for synthesis of perovskite oxides) Metal Silicides for Thermoelectric Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 (A selection of transition metal silicides for thermoelectrics) Chalcogenide Thermoelectric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 (Metal tellurides, selenides, and sulfides for thermoelectrics) Materials for Synthesis of Silicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 (A selection of high purity metals for synthesis of metal silicides) Sputtering Targets and Pellets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 (Materials for sputtering thin films of metals and metal oxides) High-purity Metal Foils for Physical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 (A collection of high purity metal foils of different thickness) Metal Slugs for Thermal Evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 (A list of high purity metals as evaporation slugs) Phosphor Host Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 (A list of metal oxides, alkoxides, acetylacetonates and salts) Phosphor Activator Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 (Rare earth oxides and salts for luminescent applications) Materials for Inorganic Photovoltaics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 (A list of metal chalcogenides and salts for inorganic photovoltaics) Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 (CdS and CdSe core-type quantum dots of different particle size and quantum yields)
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Materials Science
91
Lassi Karvonen, Petr Tome, Anke Weidenkaff* Laboratory for Solid State Chemistry and Catalysis Department of Mobility, Energy and Environment EMPA-Swiss Federal Laboratories for Materials Science and Technology berlandstrasse 129, CH-8600 Dbendorf, Switzerland *Email: anke.weidenkaff@empa.ch
p-type
h+ I +
Figure 1. A schematic diagram of a thermoelectric generator, consisting of n- and p-type legs coupled electrically in series and thermally in parallel.
92
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ZT
p-type
500
700
900
1100
1300
T (K)
[16] [17] [8] [18] [19] [20] Sr0.9Dy0.1TiO3 Zn0.98Al0.02O CaMn0.98Nb0.02O3 Sr0.9La0.1TiO3 SrTi0.9Nb0.2O3 In1.8Ge0.2O3 multiphase
composite
n-type
ZT
500
700
900
1100
1300
T (K)
Figure 2. Figure of Merit (ZT) of selected oxide materials.
As mentioned above, the layered complex oxides, such as Na0.50CoO221 and the extended family of misfit-layered oxides [MmA2O m+2]RSq [CoO2]H (M = Co, Bi, Pb, Tl, etc.; A = Ca, Sr, Ba, etc.; m = 0, 1, 2; q 0.5),22 have presented the highest ZT values for the oxides. In addition to being relatively good electrical conductors, the main reason for their performances are their high Seebeck coefficients (80 V K-1 < S < 170 V K-1) when compared to the conductivity due to a large spin- and orbital entropy of the tetravalent low-spin cobalt (Co4+) in the [CoO2] layer block.23 Zinc oxide (Aldrich Prod. No. 204951), also known as a transparent conducting oxide (TCO) material, has received notable attention as a potential thermoelectric material. For example, Zn0.98Al0.02O thin films have shown a reasonably high ZT ~ 0.3 at T = 1273 K.24 This is mainly due to enhancement of the electrical conductivity, which is more than three orders of magnitude higher than the value of the unsubstituted material. ZT also benefits the Seebeck coefficient by staying at rather elevated values, such as S > 100 V K-1 at 300 K < T < 1273 K, despite the charge-carrier doping through aluminum substitution. The major advantages of the perovskites are their profound flexibility in terms of the constituent elements covering most of the periodic table, which provides a broad selection of material-property combinations to explore. While simple perovskite-type compounds with high Seebeck coefficients are normally good insulators and, as such, not very strong potential thermoelectric materials, fruitful compromises between the lowered S and are achievable through aliovalent cation substitutions. The S2/ factor inside the ZT equation, commonly known as the power factor, is maximized by introducing charge carriers.25-27
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93
The highest ZT values, ranging between 0.3 and 0.4, are reached normally at low substitution levels (x, y < 0.2). As an extreme example, only x = 0.02 is necessary in order to reach the maximum ZT for the CaMn1-xNbxO3 system, beyond which the ZT value begins to decrease. Such a low substitution level sets requirements concerning the homogeneity of the unsintered solid-state precursor material, as spatial fluctuations with the chemical composition across the sintered body easily lead to unpredictability and instability of the properties of the sintered bodies from one synthesis batch to another. In such cases, softchemical procedures are favored, where initial mixing of the constituent cations takes place in solutions of strong organic chelating agents (e.g., EDTA, citric acid) conserving the homogeneous cation mixture over the subsequent drying, charring, and calcinations steps (Figure 3) down to the atomic scale.8
Polymerizing: 4 h @ 80 C Drying & Charring: 100 C slowly 300 C Keep 12 h @ 300 C, air Xero-gel Calcination: 510 h @ 8001,000 C, air
While the power factor can be significantly improved through substitutions, the persistent high value of has hindered the ZT from reaching values much above 0.3. Substitution by heavier cations has an observable effect, but the structural distortions reducing the electronic performance tend to outweigh the benefits. In terms of thermalconductivity suppression, the shortcomings with the perovskite lattice arise from its relatively high structural isotropicity. As compared to a typical phononic mean free path length of a few hundreds of angstroms, simple perovskites are described by translational periodicities of a few angstroms. In order to improve phononic scattering, intrinsic longer-range discontinuities, interfaces, and grain boundaries with intervals approaching the phonon, mean-free path lengths should thus be introduced. Much work on the nanostructurization has been done lately,19 and several ideas, such as using layered perovskite derivatives and artificial layered superlattice structures, are currently under development or being implemented. Additionally, a nanostructurization approach aiming at a network of charge-carrier doped interfaces in an insulating matrix that presents thicknesses of only a few unit cells is expected to provide a massive improvement to the Seebeck coefficient through increased density of states at Ef due to quantum confinement. A recent highlight that proves the concept is the observation of ZT ~ 2.4 at 300 K in an artificially grown superlattice, where a single layer of SrTi0.8Nb0.2O3 is sandwiched between several layers insulating SrTiO3. A shortcoming of the approach is that the insulating matrix accounts for most of the material, thereby returning the ZT of the entire superlattice back below 0.3.31
Milling Pelletizing: 1,0002,000 bar isostatic pressing Sintering: 1224 h @ 1,0001,200 C, air
Figure 3. Flow-sheet describing a typical soft-chemical synthesis procedure for producing oxide thermoelectric materials.
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n-type CaMn0.98Nb0.02O3-5
A)
3.5
0.08
B)
Electrical Resistivity (m cm)
The resistivity of CaMn0.98Nb0.02O3 (Figure 4B, top) indicates metal-like temperature behavior (d/dT > 0) with a steady decrease of the Seebeck coefficient, whereas semiconducting-like behavior (d/dT < 0) with relevantly higher resistivity is observed for GdCo0.95Ni0.05O3 (Figure 4B, bottom). The slope of the GdCo0.95Ni0.05O3 Seebeck coefficient features a down-turn also related to the spin-state transition, as described above (Figure 4C, bottom). Both materials show similar ZT values at a range of T < 600 K. However, at T > 600 K, the slope of the GdCo0.95Ni0.05O3 turns negative because the more negative slope of the Seebeck coefficient degrades the performance of the generator at T > 600 K. Furthermore, the high electrical resistivity of GdCo0.95Ni0.05O3 at T < 600 K keeps the total internal resistance of the module high and also within a lowtemperature range.
0.09 0.08 0.07 0.06 0.05
ZT of n-type ZT of p-type s of n-type s of p-type
C)
Seebeck Coefficient (V K-1)
ZT
0.04 0.03
T (K)
A)
Total Thermal Conductivity (W m-1K-1)
3.5 3.0 2.5 2.0 1.5 1.0 0.5 500 100 50 10 5 1 300 200 100 0 300
0.8
300
400
500
600
700
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0.0
p-type CdCo0.95Nb0.05O3-5
T (K )
Figure 5. Figure of Merit (ZT) and thermoelectric compatibility factor (s) of the p-type GdCo0.95Ni0.05O3 and the n-type CaMn0.98Nb0.02O3 materials.
B)
Electrical Resistivity (m cm)
The thermoelectric compatibility factors of CaMn0.98Nb0.02O3 and GdCo0.95Ni0.05O3 are presented in Figure 5. Difference by s factor of 2-4 indicates a notably low expectable output. To overcome the difference in compatibility factors, an alternative p-type material, La1.98Sr0.02CuO4, was tested instead of the GdCo0.95Ni0.05O3 material. CaMn0.98Nb0.02O3 (n-type)/La1.98Sr0.02CuO4 (p-type) The thermoelectric properties of the materials are summarized in Figure 6.
A)
(W m-1 k-1)
3.5 3.0 2.5 2.0 1.5 1.0 0.5 n-type - CaMn0.98Nb0.02O3 p-type - La1.98Sr0.02CuO4
C)
Seebeck Coefficient (V K-1)
400
500
600
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800
T (K)
Figure 4. Temperature dependence of the thermoelectric properties A) , B) and C) S of n-type CaMn0.98Nb0.02O3 (top panel) and p-type GdCo0.95Ni0.05O3 (bottom panel).
B)
(mcm)
60 50 40 30 20 10 300
The = ph + el of both materials (Figure 4A) are close to 3 Wm K above 300 K. The thermal conductivity of the GdCo0.95Ni0.05O3 leg (Figure 4A, bottom) increases by 50 % and is between 600 K and 800 K; this is attributed to an increase in the electronic part (el) due to a spinstate transition increasing the charge carrier mobility - fairly typical for the LnCoO3-based systems. On the other hand, the CaMn0.98Nb0.02O3 leg (Figure 4A, top) shows a monotonic decrease in thermal conductivity over the observed temperature scale, which is understood to arise dominantly from the phononic part of the thermal conductivity (ph).
-1 -1
C)
S(V K-1)
200 100 0 -100 -200 -300 300 400 500 600 700 800
T (K)
Figure 6. Temperature dependence of A) , B) and C) S of the p-type La1.98Sr0.02CuO4 and the n-type CaMn0.98Nb0.02O3 materials.
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s ( V -1 )
95
The thermal conductivities (Figure 6A) and resistivities (Figure 6B) of both materials are similar in terms of magnitude and trend. Both appear to show metallic behavior and large Seebeck coefficients (Figure 6C). The temperature dependence of the ZT (Figure 7) is sensitive to the Seebeck coefficient of La1.98Sr0.02CuO4, which is manifested by the degradation of the ZT value above T > 400 K. The temperature dependence of the compatibility factors (Figure 7) indicates a closer similarity (s < 2) at a lower-temperature regime (300 K < T < 500 K). At T > 500 K, a decrease in the conversion efficiency of the four-leg modules was observed. Although the gross ZT characteristics of La1.98Sr0.02CuO4, are poorer compared to the GdCo0.95Ni0.05O3, a significant improvement due to a better compatibility delivered by similar electrical and thermal conductivities (Figure 6C) can be observed.
0.09 0.08 0.07 0.06 0.05
ZT of n-type ZT of p-type s of n-type s of p-type
Acknowledgments
The Swiss Federal Office of Energy (SFOE), the Swiss National Science Foundation (SNF-MANEP), and Swisselectric are highly acknowledged for financial support. K. Koumoto, A. Maignan, and J. Hulliger are acknowledged for their fruitful discussions and scientific input. We also gratefully acknowledge the present and former members of the Solid State Chemistry and Catalysis lab at EMPA for their experimental results.
References
(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) CRC Handbook of Thermoelectrics; Rowe, D. M., Ed.; CRC Press: Boca Raton, 1995. Tritt, T. M. Science 1999, 283, 804. DiSalvo, F. J. Science 1999, 285, 703. Weidenkaff, A.; Robert, R.; Aguirre, M. H.; Bocher, L.; Lippert, T.; Canulescu, S. Renewable Energy 2008, 33, 342. Tome, P.; Robert, R.; Trottmann, M.; Bocher, L.; Aguirre, M. H.; Hejtmanek, J.; Weidenkaff, A. J. Electr. Mater. 2010, 39, 1696. Tome , P.; Suter , C.; Trottmann , M.; Steinfeld A.; Weidenkaff, A. J. Mat. Res. 2011, 26, 1975. Ohta, S.; Ohta, H.; Koumoto, K. J. Ceram. Soc. Jpn. 2006, 114, 102. Bocher, L.; Aguirre, M. H.; Logvinovich, D.; Shkabko, A.; Robert, R.; Trottmann, M.; Weidekaff, A. Inorg. Chem. 2008, 47, 8077. Fujita, K.; Mochida, T.; Nakamura, K. Jpn. J. Appl. Phys. 2001, 40, 4644. Shikano, M.; Funahashi, R. Appl. Phys. Lett. 2003, 82, 1851. Funahashi, R.; Shikano, M. Appl. Phys. Lett. 2002, 81, 1459. Robert, R.; Aguirre, M. H.; Hug, P.; Reller, A.; Weidenkaff, A. Acta Mater. 2007, 55, 4965. Mikami, M.; Funahashi, R.; Yoshimura, M.; Mori, Y.; Sasaki, T. J. Appl. Phys. 2003, 94, 5144. Xu, G.; Funahashi, R.; Shikano, M.; Matsubara, I.; Zhou, Y. Appl. Phys. Lett. 2002, 80, 3760. He, T.; Chen, J.; Calvarese, T. G.; Subramanian, M. A. Solid State Sci. 2006, 8, 467. Muta, H.; Kurosaki, K.; Yamanaka, S. J. Alloys Compd. 2003, 350, 292. Ohtaki, M.; Tsubota, T.; Eguchi, K.; Arai, H. J. Appl. Phys. 1996, 79, 1816. Liu, J.; Wang, C. L.; Su, W. B.; Wang, H. C.; Zheng, P.; Li, J. C.; Zhang, J. L.; Mei, L. M. Appl. Phys. Lett. 2009, 95, 162110. Koumoto, K.; Wang, Y.; Zhang, R.; Kosuga, A.; Funahashi, R. Annu. Rev. Mater. Res. 2010, 40, 363. Brardan, D.; Guilmeau, E.; Maignan, A.; Raveau, B. Solid State Commun. 2008, 146, 97. Terasaki, I. Phys. Rev. B. 1997, 56, R12685. Yamauchi, H.; Karvonen, L.; Egashira, T.; Tanaka, Y.; Karppinen, M. J. Solid State Chem. 2011, 184, 64. Koshibae, W.; Tsutsui, K.; Maekawa, S. Phys. Rev., B. 2000, 62, 6869. Tsubota, T.; Ohtaki, M.; Eguchi, K.; Arai, H. J. Mater. Chem. 1997, 7, 85. Maignan, A.; Hebert, S.; Li, P.; Pelloquin, D.; Martin, C.; Michel, C.; Hervieu, M.; Raveau, B. Crystal Engineering 2002, 5, 365. Robert, R.; Bocher, L.; Sipos, B.; Dbeli, M.; Weidenkaff, A. Prog. Solid State Chem. 2007, 35, 447. Bocher, L.; Aguirre, M. H.; Robert, R.; Logvinovich, D.; Bakardjieva, S.; Hejtmanek, J.; Weidenkaff, A. Acta Mater. 2009, 57, 5667. Uchida K.; Tsuneyuki S.; Schimizu T. Phys. Rev. B. 2003, 68, 174107. Frederikse H. P. R.; Thurber W. R.; Hosler W. R. Phys. Rev. 1964, 134, A442. Ohta, S.; Nomura, T.; Ohta, H.; Hirano, M.; Hosono, H.; Koumoto, K. Appl. Phys. Lett. 2005, 87, 092108. Ohta H. Mater. Today 2007, 10, 44. Snyder, G. J. Appl. Phys. Lett. 2004, 84, 2436.
0.04 0.03 0.02 0.01 0.00 300 400 500 600 700 800
0.00
T (K)
Figure 7. Temperature dependence of the Figure of Merit (ZT) and thermoelectric compatibility factor (s) of the p-type La1.98Sr0.02CuO4 and the n-type CaMn0.98Nb0.02O3 materials.
Summary
Thermoelectric heat-to-electricity conversion has received increasing attention over the past 15 years as one of the ways to improve the energy efficiency of the conventional electric-power production strategies. Thanks to their flexibility, perovskite-oxide materials and derivatives offer a wide range of possibilities to search and optimize novel thermoelectric materials. The advantages of the perovskites are their profound flexibility and relatively simpleand therefore predictablestructure-property relations. On the other hand, the simplicity of the perovskite structure can be seen as a challenge when considering the ways to suppress thermal conductivity. Despite lower performance compared to more conventional thermoelectric materials, such as chalcogenides, the all-oxide materials have their undisputable strengths, such as being able to operate at much higher temperatures and oxidizing atmospheres.
Calcium chloride hexahydrate Calcium chloride Calcium hydroxide Calcium isopropoxide Calcium methoxide
s (V1)
98%
ZT
99.99% trace metals basis 99.995% trace metals basis 99.9% trace metals basis 97%
96
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Purity 99.997% trace metals basis 99.995% trace metals basis 99.9% trace metals basis
Prod. No. 202967-10G 202967-50G 229539-5G 229539-50G 208159-25G 208159-100G 208159-500G 86910-250ML 86910-1L 451738-1G 451738-5G 514381-1G 514381-5G 481033-10G 481033-50G 244112-5G 244112-100G 244112-500G 244112-2KG 244759-50G 244759-250G 377996-5ML 377996-25ML 377996-100ML 463582-25G 204730-5G 204730-25G 204757-25G 204757-125G 248576-100G 248576-1KG 248576-10KG 462551-25ML 462551-50ML 377449-250G 377449-1KG 450995-5G 450995-25G 429449-5G 429449-25G 203742-25G 203742-100G 431761-1G 431761-10G 463701-5G 463701-25G 379956-5G 409332-1G 409332-5G 342440-250G 203106-10G 203106-50G 529443-5G 529443-25G 544183-250G-A 544183-1KG-A 203866-5G 203866-25G 203866-125G 451193-5G 451193-25G 283622-5G 283622-250G 283622-1KG 203874-20G 203874-100G 203874-500G 481793-5G 481793-25G 203882-20G 203882-100G
Titanium(IV) butoxide Titanium(II) chloride Titanium(III) chloride Titanium(III) oxide Titanium(IV) butoxide
97.0%, gravimetric 99.98% trace metals basis 99.995% trace metals basis 99.9% trace metals basis 97%
Ti(OC2H5)4 Ti[OCH(CH3)2]4
liquid liquid
Titanium(IV) methoxide Titanium(IV) oxide, rutile Titanium(IV) oxide, rutile Titanium(IV) oxide, anatase
99.99% trace metals basis 99.995% trace metals basis 99.99% trace metals basis 99% trace metals basis
Titanium(IV) tert-butoxide Manganese(II) carbonate Manganese(II) chloride Manganese(II) chloride Manganese(II) nitrate hydrate Manganese(II) oxide Manganese(III) oxide Cobalt(II) carbonate hydrate Cobalt(II) chloride Cobalt(II) hydroxide Cobalt(II) nitrate hexahydrate Cobalt(II) oxide Nickel carbonate, basic hydrate Nickel(II) chloride hexahydrate
Ti[OC(CH3)3]4 MnCO3 MnCl2 MnCl2 Mn(NO3)2xH2O MnO Mn2O3 CoCO3xH2O CoCl2 Co(OH)2 Co(NO3)2 6H2O CoO NiCO3 2Ni(OH)2 xH2O NiCl2 6H2O
99.9% trace metals basis 99.999% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.995% trace metals basis 99.998% trace metals basis 99.999% trace metals basis 95% 99.999% trace metals basis 99.99% trace metals basis 99.999% trace metals basis
liquid powder beads beads crystals and lumps powder and chunks solid powder beads powder crystals and lumps powder powder crystals and lumps
NiCl2 Ni(OH)2
powder powder
Ni(NO3)2 6H2O
solid
NiO NiO
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Purity 99.99% trace metals basis 99.995% trace metals basis 99.999% trace metals basis 99.995% trace metals basis 97% 99.999% trace metals basis
Form beads powder powder powder powder solid crystals and lumps
Prod. No. 651745-5G 651745-25G 229628-10G 229628-100G 203149-10G 203149-50G 451665-5G 451665-25G 289787-250G 289787-1KG 332666-5G 229636-5G 229636-25G 229636-100G 204455-5G 204455-25G 204455-100G 472018-100G 472018-500G 204463-10G 204463-50G 451282-5G 439665-5G 439665-25G 463752-5G 463752-25G 463752-100G 440698-5G 440698-25G 204498-10G 204498-50G 415138-10G 415138-50G 383163-5G 510696-5G 510696-25G 336602-10G 336602-50G 339202-5G 339202-50G 203920-10G 203920-50G 203920-250G 206229-1G 206229-5G 206229-25G 238058-1G 238058-5G 203556-100G 199923-100G 199923-500G 325767-100G 203521-25G 203521-100G 449830-5G 449830-25G 447226-50G 203548-25G 203548-100G 203548-500G 331937-5G 331937-100G 331937-500G 431850-1G 431850-5G 203254-1G 203254-5G 203254-25G
Strontium carbonate
SrCO3
Strontium carbonate Strontium chloride hexahydrate Strontium chloride Strontium chloride Strontium hydroxide octahydrate
99.9% trace metals basis 99.995% trace metals basis 99.995% trace metals basis 99.99% trace metals basis 99.995% trace metals basis
Strontium isopropoxide Strontium nitrate Strontium oxide Niobium(IV) oxide Niobium(V) chloride Niobium(V) chloride Niobium(V) ethoxide Niobium(V) oxide
99.9% trace metals basis 99.995% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.995% trace metals basis 99.9% trace metals basis 99.95% trace metals basis 99.99% trace metals basis
crystalline powder crystals and lumps powder powder powder crystals and lumps liquid powder
RuCl3 xH2O
Ruthenium(IV) oxide Lanthanum(III) oxide Lanthanum(III) oxide Lanthanum(III) carbonate hydrate Lanthanum(III) chloride heptahydrate Lanthanum(III) chloride Lanthanum(III) hydroxide Lanthanum(III) nitrate hexahydrate
RuO2 La2O3 La2O3 La2(CO3)3xH2O LaCl3 7H2O LaCl3 La(OH)3 La(NO3)3 6H2O
99.9% trace metals basis 99.999% trace metals basis 99.99% trace metals basis 99.9% trace metals basis 99.999% trace metals basis 99.99% trace metals basis 99.9% trace metals basis 99.999% trace metals basis
powder and chunks powder powder powder solid beads powder solid
La(NO3)3 6H2O
solid
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Name Europium(III) chloride Europium(III) nitrate hydrate Europium(III) oxide Europium(III) oxide Bismuth(III) chloride Bismuth(III) chloride Bismuth(III) chloride Bismuth(III) oxide
Composition EuCl3 Eu(NO3)3 xH2O Eu2O3 Eu2O3 BiCl3 BiCl3 BiCl3 Bi2O3
Purity 99.99% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.999% trace metals basis 99.99% trace metals basis 99.999% trace metals basis
Form powder solid powder and chunks powder beads powder solid powder
Prod. No. 429732-1G 429732-5G 254061-1G 254061-10G 323543-1G 323543-5G 203262-5G 203262-25G 470279-5G 470279-25G 450723-5G 450723-25G 254142-25G 254142-125G 202827-10G 202827-50G 202827-250G 223891-100G 223891-500G
Bismuth(III) oxide
Bi2O3
powder
More than 40,000 research chemicals and Materials Science products Over 4,000 innovative new products 10,000 chemical structures 8,500 updated literature citations Extensive chemical and physical data
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76999
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Mikhail I. Fedorov,* Vladimir K. Zaitsev Ioffe Physical-technical Institute, St. Petersburg, Russia *Email: m.fedorov@mail.ioffe.ru
Introduction
In recent years, the price of tellurium, a key component in the bestperforming thermoelectric materials, has increased significantly, leading to the question, Is it economically viable to produce thermoelectric generators on an industrial scale?. The main thermoelectric generator material is bismuth telluride, which has a high enough dimensionless figure of merit (ZT ~ 1) at room temperature to be practical for energy generating applications. The dimensionless figure of merit is described as: ZT = S2T/ where S is the Seebeck coefficient, and are the electrical and thermal conductivities, respectively, and T is the absolute temperature. The other materials used for higher operating temperatures are PbTe for n-type and GeTe for p-type semiconductors. Both these materials are expensive, especially GeTe. Due to increasing tellurium costs, it is necessary to find alternative materials that have comparable figures of merit. Silicides represent a group of promising thermoelectric materials, for several reasons: silicon is the fourth most abundant element and among the most widespread elements of the Earths crust; furthermore, silicides do not contain toxic elements, are ecologically benign, and represent various mechanisms of electron transport. The main characteristics of silicides are presented in Table 1, which show the latest results obtained in the field of thermoelectrics.1,2
Table 1. Important parameters of several silicide thermoelectrics.
Material CrSi2* MnSi1.7 FeSi2 Ru2Si3 ReSi1.75 CoSi Mg2(Si,Sn) Melting Point, K 1763 1430 1490 1970 2213 1700 10511375 Eg, eV 0.7 0.66 0.87 1.1 0.15 0.016 0.360.77 ZTmax 0.25 (p) 0.9 (p)8 0.4 (n)9; 0.2 (p) 0.4 (n); 0.3 (p) 0.8 (p) 0.2 (n) 1.2 (n)4; 0.5 (p)8
1,2
Figure 1. Left) Traditional thermoelement with n- and p-type legs. Right) Thermoelement with an anisotropic material.
~45013
The left scheme shows a traditional thermoelement, consisting of two legs with different types of conductivity (n and p). The right scheme shows another type of thermoelement, which includes a material with an anisotropic Seebeck coefficient. Here, the voltage of the thermoelement is determined by the difference of longitudinal and transverse Seebeck coefficients. The thermoelectric figure of merit for this case (ZTa) may be written as:
ZTa = (SySz)2y/y (1+z/y)(1+y/z) T
where symbols || (along the axis of higher symmetry) and (across the same axis) denote the direction used to measure this property. In this type of thermoelement, voltage is shown as: V=1/2(S||-S)Tl/d
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N, 10-4Wm-1K-2
where V - is the voltage of the thermoelement, T is the temperature differential, l - is the length between contacts, and d - is the thickness of the element. Taking into account that T is closely related to the thickness of the element, it is possible to use the following expression for volt/watt sensitivity: V/Q=1/2(S||-S)/h/45 where Q is the heat flux through the thermoelement, 45 is the average thermal conductivity at an angle of 45 to the axis of higher symmetry, and h is the width of the strip of thermoelectric material. This formula is valid when contact resistance is much lower than the resistance of the strip. The main advantage of this kind of thermoelement is the absence of contacts in the hot junctions.
70 60 50
40 30 20 10 0 300
Synthesis of Silicides
As discussed previously, silicides are a promising group of nontoxic and cost-efficient materials for thermoelectrics. These materials can be prepared by a variety of methods, particularly those that allow for property measurements. For example, chromium disilicide, higher manganese silicide, ruthenium sesquisilicide, and cobalt monosilicide are prepared by either the Bridgman or Czochralski methods of single crystal preparation. The Czochralski method has also been used for the preparation of rhenium silicide. The floating zone method is also used to synthesize many silicides, especially for refractory types. In laboratory studies of the physical properties of thermoelements, magnesium silicide-based materials are prepared by direct melting of components with subsequent annealing steps.
1.2 1.0 0.8 0.6 0.4 0.2 Mg2(Si, Sn) MnSi1.7(opt) CoSi CrSi2 ||C
0.0 300
ZT
500
700
T, K
Interest in the use of chromium disilicide started following an attempt to produce the silicide by high-temperature flux growth in molten tin.3 Needles formed by this method retained tin within their structure. After etching the tin, the final product contained channels with internal diameters of approximately 100 m (Figure 4). The structural anisotropy is reflected within the varying properties between parallel and perpendicular directions.
Figure 4. SEM micrograph of CrSi2 tubes obtained from flux growth in molten tin illustrating the hollow interior.
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The most efficient thermoelectric material among all transition metal silicides is higher manganese silicide. It has a figure of merit significantly lower than that of Mg2Si-based materials, but is still in the region of ZT ~ 0.9 at 870 K. The best material has to be doped in a complex manner to produce the highest value for figure of merit. The material must contain at least three dopants: one to reduce thermal conductivity, one to optimize the crystalline lattice, and another to optimize the charge carrier density. In an idealized response, the material will have the characteristics shown in Figure 3 for Mg2(Si,Sn). In comparison with Mg2Si-based materials, higher manganese silicide has greater mechanical and chemical strength, which allows its use in air and aggressive media with a limited amount of protection.
In this system, it is difficult to produce a p-type material with a ZT > 0.5,4 due to the position of the valence band in the -point of the Brillouin zone and a relatively low energy gap in Mg2Sn.
Conclusions
Thermoelectrical research could benefit greatly from a single rule to determine the most appropriate material for a given application. Unfortunately, no such method exists, so all cases require examination of the interactions between many parameters, and it is not always possible to determine the optimal material constituents. As shown above, the higher transition metal silicides are very well-suited for anisotropic thermoelectric conversion. Essential anisotropy of Seebeck coefficient, together with good mechanical properties, allows production of reliable anisotropic thermoelectric converters. For traditional thermoelectric modules, the situation is different. There is no coupling of the materials that have high ZT values for both signs. In this case, it is necessary to produce a thermoelectric generator comprising significantly different materials that may result in the device having low reliability.
References
(1) Fedorov, M. I.; Zaitsev, V. K. Thermoelectrics Handbook. Macro to Nano; Rowe, D. M., Ed.; CRC press. Taylor & Francis group, Boca Raton-London-New York, 2006; pp 311-31-19. Zaitsev, V. K.; Fedorov, M. I.; Eremin, I. S.; Gurieva, E. A. Thermoelectrics Handbook. Macro to Nano; Rowe, D. M., Ed.; CRC press. Taylor & Francis group, Boca RatonLondon-New York, 2006; pp 29-1-29-11. Solomkin, F. Yu.; Suvorova, E. I.; Zaitsev, V. K.; Novikov, S. V.; Burkov, A. T.; Samunin, A. Yu.; Isachenko, G. N. Tech. Phys. 2011, 81, 147. Fedorov, M. I.; Zaitsev, V. K.; Isachenko, G. N. Solid State Phenomena, 2011, 170, 286. Hesse, J. Z. Angew. Phys. 1969, 28, 133. Takeda, M.; Kuramitsu, M.; Yoshio, M.; Thin Solid Films 2004, 461, 179. Andreev, A. A.; Fedorov, M. I.; Ivanov, Yu.V.; Petrova, V.S.; Zaitsev, V. K. J. of Electronic Mater. 2011, 40, 1485. Simkin, B. A.; Hayashi, Y.; Inui H. Intermetallics, 2005, 13, 1225. Gu, J.-J.; Oh, M.-W.; Inui, H.; Zhang, D. Phys. Rev. B, 2005, 71, 113201. Zaitsev, V. K.; Fedorov, M. I.; Gurieva, E. A.; Eremin, I. S.; Konstantinov, P. P.; Samunin, A. Yu.; Vedernikov, M. V. Phys. Rev. B. 2006, 74, 045207. Voronov, B. K.; Dudkin, L. D.; Trusova, N. N. Chemical bond in semiconductors, 1969, pp 291-298 (in Russian). Isoda, Y.; Nagai, T.; Fuziu, H.; Imai, Y.; Shinohara, Y. Proceedings of ICT06 2006, IEEE, pp 406. Isoda, Y.; Nagai, T.; Fujiu, H.; Imai, Y.; Shinohara Y. Proceedings of ICT07 2008, IEEE, pp 251. Zhang, Q.; He, J.; Zhu, T. J.; Zhang, S. N.; Zhao, X. B.; Tritt, T. M. Appl. Phys. Lett. 2008, 93, 102109.
(2)
(3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13)
(14)
Figure 5. Figures of merit for solid solutions of Mg2Si and Mg2Sn. 1) Mg2Si0.4Sn0.6 <Sb>;10 2) Mg2Si0.4Sn0.6 <Bi>;10 3) Mg2Si0.36Ge0.04Sn0.6;10 4) Mg2Si0.5Sn0.5;12 5) Mg2Si0.5Sn0.5;13 6) Mg2Si0.4Sn0.6.14
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Cr Cr Mn Mn Fe Fe Fe
99.95% 99.995% trace metals basis 99% 99.99% trace metals basis 99.98% trace metals basis 99.995% trace metals basis 99.99% trace metals basis
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Name Iron
Composition Fe
Form powder
Prod. No. 267953-5G 267953-250G 267953-1KG 266213-30G 266213-150G 266256-3.1G 266256-15.5G 263230-10G 263230-50G 203343-1G 203343-5G 203343-25G 327395-5G 327395-25G 203351-10G 203351-50G 545023-1G 545023-5G 209694-5G 204188-5G 449482-6.9G 357111-200MG 14507-100G-R 14507-250G-R 14507-6X250G-R 14507-1KG-R 14507-6X1KG-R 265659-100G 265659-250G 265632-100G 265632-500G 204692-10G 356956-7G
Fe Fe Ge Ge
99.98% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.999% trace metals basis
Ge Ge Ru Ru Re Re Re Sn
99.999% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.9% trace metals basis 99.995% trace metals basis 99.99% trace metals basis 99.9% trace metals basis -
Sn Sn Sn Sn
99.999% 99.8% trace metals basis 99.999% trace metals basis 99.999% trace metals basis
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Materials Science
Well-defined problem?
No
R. Bruce van Dover Department of Materials Science and Engineering Cornell University Ithaca, NY 14853-1501 Email: rbv2@cornell.edu
No
No
Yes
Yes
No
Yes
No
Yes
No
No
Figure 1. Is the combinatorial/high-throughput approach the right choice to find a new material that can solve an outstanding problem? This decision tree illustrates some of the key questions that should be asked. When the right conditions are met, highthroughput experiments can be impressively effective.
Many methods for high-throughput synthesis have been developed,2,3 but the Codeposited Composition Spread (CCS) technique has proven to be an especially versatile method for forming a wide range of compositions in a single experiment. In this method, thin films are deposited by physical vapor deposition on a substrate simultaneously, from two or more sources that are spatially separated and chemically distinct, producing a film with an inherent composition gradient and intimate mixing of the constituents. With three sources, an entire ternary phase diagram may be produced in a single experiment. Composition spreads may also be synthesized using a traveling shutter4 or shaped mask5 to create a film with a thickness gradient (wedge). A composition gradient can then be obtained by rotating the sample with respect to the shutter and depositing a new overlapping wedge of a second or third film. Atomic mixing is achieved by depositing many wedges each of submonolayer thickness. This approach has the advantage of the composition/position dependence being well-defined (ignoring resputtering effects), although surface reorganization during the short time between wedge depositions can lead to adventitious artifacts.
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CCS synthesis is distinct from conventional combinatorial chemistry as employed, for example, in drug discovery6 as well as the discrete combinatorial synthesis (DCS) approach pioneered by Xiang and Schultz.7 In the latter, mixtures of inorganic components are created by sequential deposition of discrete layers of precursors followed by moderate- or high-temperature diffusion and reaction steps. An important advantage of the DCS technique is that arbitrary compositions with a large number of constituents can be prepared as desired. A key advantage of the composition-spread approach is the opportunity to prepare materials with no subsequent processing, which means that low-temperature or metastable phases may be prepared. The CCS approach also allows properties to be determined with very fine composition resolution, often limited by the resolution of the property measurement itself. For example, it is generally straightforward to sample composition space at 1 mol% intervals, equivalent to investigating thousands of materials in a single experiment. The CCS technique has been used to create both alloys and compounds in chemical systems, including intermetallics, nitrides, oxides, and carbides. A large number of thin film deposition techniques are available for synthesis of composition spread thin films, including evaporation,8,9 sputtering,10-12 pulsed-laser deposition (PLD),13 chemical vapor deposition,14 and cold-plasma processing,15 among others. Of these, sputtering offers a unique combination of advantages: In most cases sputtering rates are constant and reproducible16 when powered by modern dc, rf, or pulsed-dc regulated power supplies, allowing composition spreads with a targeted range of compositions to be synthesized. When magnetron sputter guns are used for sputtering there is little interaction between the sources. That is, the deposition rate from one gun is independent of the operation of the other guns. As a result the composition profile (composition of the codeposited film as a function of position on the substrate) can be predicted quantitatively once the deposition rate for each individual source is determined. However, in some circumstances the magnetron gun may interact significantly with the growing films, leading to resputtering and deviation of the composition from that predicted by simple summation of independent deposition rates. This effect can be predicted quantitatively using known sputter yields and the conditions of the sputter system, leading to accurate adjustments and an excellent quantitative prediction of the composition. The composition gradients achieved by codeposition (using two-inchdiameter sources) are typically about 1 atomic percent per mm, a convenient scale that allows many measurement techniques to resolve trends with about 1 atomic percent resolution. Sputtering is convenient for deposition of metals, oxides (by reactive sputtering in an oxygen-containing ambient), nitrides (sputtering in Ar-N2), carbides (sputtering Ar-CH4), and mixed anion (e.g., oxynitride) systems. Targets of most metals and many unary and binary oxides are readily available, along with many other common materials. Sputter codeposition also has inherent disadvantages, including: It is not simple to change the composition gradient. The gradient is affected by changing the total inert gas pressure in the system, but many other aspects of sputtering change as well, confounding systematic studies. Targets of the alkali metals, alkaline earth metals, and the lighter lanthanide metals are problematic, due to rapid oxidation/hydrolysis/ hydration of the metal target in air. Determining the structure of the materials formed in a composition spread is important for understanding composition/property relations. Thin films are well suited for X-ray diffraction studies for phase identification. Using automated data acquisition, in either a conventional stationary-anode diffractometer17 or a synchrotron-based system,18 hundreds of diffraction patterns can be acquired on a single
composition-spread substrate. An unsolved challenge is to develop automated techniques for the identification of unique diffraction patterns and clustering these into contiguous phase fields corresponding to regions (compositions) of the CCS film. Some progress has been made in this respect,17,19 but a fully robust algorithm has yet to be developed.
Pt
320 300 280 260 240 220 200 180 160 140 120 100
E1/2 >500 mV
0.1
0.2
0.3
0.4
0.5
0.6
0.7
x in Pt1-x Tax
Figure 2. The catalytic activity of Pt-Ta compositions is measured using a fluorescence test: a lower half-wave potential, E1/2, implies greater activity for methanol oxidation. This plot shows that strong activity is associated with the presence of the orthorhombic Pt2Ta phase, is best in the single phase region (18 -35 at% Ta), and is optimized at the composition Pt0.71Ta.29, close to the stoichiometric value.24
Figure 2 shows that the fine compositional resolution offered by the CCS technique permits two important conclusions about the internal consistency of the data. First, the close agreement between values at adjacent compositions indicates that random variations in the measurement are small compared to the overall trend. Second, the smooth trend with composition in the Pt2Ta phase field allows the optimum composition to be identified with confidence. Internal consistency does not prove that the data is accurate in composition or in E1/2 value; the absolute accuracy must be validated by comparison
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with detailed one-off studies. The key advantage of the combinatorial method is that it allows the researcher to efficiently identify particular compositions for further study based on data rather than on conservative or radical speculation.
ZnO 1 1.25 Mobility (cm2/Vs) 1.6 2.0 2.5 3.0 4.0 5.0 6.3
Predicting catalytic properties is not reliableneither from first principles nor from accumulated experienceso catalyst development has always relied on an empirical approach. High-throughput studies have proven especially useful in facilitating rapid optimization of catalyst composition using factorial designs as well as more exotic approaches, such as genetic algorithms.25 Solution-based synthesis is often employed for optimization because it most closely approximates the processing of realistic formulations. The high-throughput approach has been applied successfully to primary screening and optimization for a wide range of catalyst functions, including polymerization catalysts, enantioselective catalysts, oxidation catalysts, reduction catalysts, dehydrogenation catalysts, and many others.
Zn0.93Al0.07O
Zn0.93In0.07O
Figure 3. ZnO with Al or In forms a transparent conductor. Compared to Zn2+, the Al3+ ion is much smaller while In3+ is much larger. Co-doping yields an average dopant size that is a better fit in the ZnO crystal, reducing scattering. A Zn-Al-In-oxide composition spread allows the effect of varying levels of both dopants to be measured. The binary spreads Zn-Al-oxide and Zn-In-oxide are prepared in separate experiments under nominally identical conditions. For a given overall doping level, the highest mobility is observed in co-doped compositions.28
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Outstanding Issues
While development of synthesis and characterization techniques is basic to the concept of high-throughput experimentation, these steps lead to data and information, not knowledge or insight. In fact, the massive quantity of data, coupled with the modest level of accuracy or precision associated with the speed/quality tradeoff, quickly leads to a new challenge-how to make use of the data. Tracking only the latest topperforming material in a high-throughput investigation discounts the insights and new directions that could be gleaned from lesserperforming materials. Efficient methods are urgently needed for transforming an overwhelmingly data-rich environment into actionable insights regarding structure-processing-property associations and relationships in materials. Machine learning and statistical approaches, such as cluster analysis and multivariate regression, are important components for this task, but they do not incorporate the relationships that are inherent in the physics and chemistry of materials. Thus, perhaps the most essential difference between conventional research and the combinatorial materials science approach is in the role of informaticsthe processing, management and retrieval of information.
Acknowledgments
This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (under Award Number DE-FG02-07ER46440). The author would like to gratefully acknowledge formative discussions with Lynn Schneemeyer, Hctor Abrua, Francis DiSalvo and John Gregoire.
References
(1) Hemminger, J.; Crabtree, G. W.; Kastner, M. "New science for a secure and sustainable energy future," Office of Basic Energy Sciences, Department of Energy, 2008. Xiang, X.-D.; Takeuchi, I., Eds. Combinatorial Materials Synthesis; Marcel Dekker: New York, 2003. High-throughput Synthesis: Principles and Practices; Marcel Dekker: New York, 2001. Xiang, X.-D. Bull. Am. Phys. Soc. 1999, 44, 103. Dahn, J. R.; Trussler, S.; Hatchard, T. D.; Bonakdarpour, A.; Mueller-Neuhaus, J. R.; Hewitt, K. C.; Fleischauer, M. Chem Mater 2002, 14, 3519. Doyle, P. M. J Chem. Tech. 1995, 64, 317. Xiang, X.-D.; Sun, X.; Briceno, G.; Lou, Y.; Wang, K.-A.; Chang, H.; Wallace-Freedman, W. G.; Chen, S.-W.; Schultz, P. G. Science 1995, 268, 1738. Kennedy, K.; Stefansky, T.; Davy, G.; Zackay, V.; Parker, E. R. J Appl Phys 1965, 36, 3808. Hammond, R. H.; Ralls, K. M.; Meyer, C. H.; Snowden, D. P.; Kelly, G. M.; Pereue, J. H., Jr. J. Appl. Phys. 1971, 43, 2407. Hanak, J. J. J. Mat. Science 1970, 5, 964. van Dover, R. B.; Hong, M.; Gyorgy, E. M.; Dillon, J. F., Jr.; Albiston, S. D. J Appl Phys 1985, 57, 3897. van Dover, R. B.; Schneemeyer, L. F.; Fleming, R. M. Nature (UK) 1998, 162. Lippmaa, M.; Koida, T.; Minami, H.; Jin, Z. W.; Kawasaki, M.; Koinuma, H. Applied Surface Science 2002, 189, 205. Smith, R. C.; Hoilien, N.; Roberts, J.; Campbell, S. A.; Gladfelter, W. L. Chem Mater 2002, 14, 474. Terajima, T.; Koinuma, H. Applied Surface Science Proceedings of the Second Japan-US Workshop on Combinatorial Materials Science and Technology 2004, 223, 259. Gregoire, J. M.; Dale, D.; Kazimirov, A.; DiSalvo, F. J.; van Dover, R. B. Journal of Vacuum Science & Technology A 2010, 28, 1279. Long, C. J.; Hattrick-Simpers, J.; Murakami, M.; Srivastava, R. C.; Takeuchi, I.; Karen, V. L.; Li, X. Review of Scientific Instruments 2007, 78. Gregoire, J. M.; Dale, D.; Kazimirov, A.; DiSalvo, F. J.; van Dover, R. B. Review of Scientific Instruments 2010, 80, 123905. Long, C. J.; Bunker, D.; Li, X.; Karen, V. L.; Takeuchi, I. Review of Scientific Instruments 2009, 80. Reddington, E.; Sapienza, A.; Gurau, B.; Viswanathan, R.; Sarangapani, S.; Smotkin, E. S.; Mallouk, T. E. Science 1998, 280, 1735. Gregoire, J. M.; Kostylev, M.; Tague, M. E.; Mutolo, P. F.; van Dover, R. B.; DiSalvo, F. J.; Abruna, H. D. J Electrochem Soc 2009, 156, 160. Strasser, P.; Fan, Q.; Devenney, M.; Weinberg, W. H.; Liu, P.; Norskov, J. K. Journal of Physical Chemistry B 2003, 107, 11013. Jayaraman, S.; Hillier, A. C. Journal of Physical Chemistry B 2003, 107, 5221. Gregoire, J. M.; Tague, M. E.; Cahen, S.; Khan, S.; Abruna, H. D.; DiSalvo, F. J.; van Dover, R. B. Chem Mater 2009, 22, 1080. Potyrailo, R. A.; Maier, W. F., Eds. Combinatorial and High-Throughput discovery and Optimization of Catalysts and Materials; Taylor & Francis: Boca Raton, 2007. Ginley, D. S.; Bright, C. MRS Bulletin 2000, 25, 15. Perkins, J. D.; del Cueto, J. A.; Alleman, J. L.; Warmsingh, C.; Keyes, B. M.; Gedvilas, L. M.; Parilla, P. A.; To, B.; Readey, D. W.; Ginley, D. S. In 2nd International Symposium on Transparent Oxide Thin Films for Electronics and Optics (TOEO-2), 8-9 Nov. 2001; Elsevier: Switzerland, 2002; Vol. 411, pp 152. Kirby, S. D.; van Dover, R. B. Thin Solid Films 2009, 517, 1958. DiSalvo, F. J. Science 1999, 285, 703. Mahan, G. D. J Appl Phys 1989, 65, 1578.
(2) (3) (4) (5) (6) (7) (8) (9) (10) (11)
Conclusions
The high-throughput approach to inorganic materials discovery improves the likelihood of discovering new materials with useful properties because it dramatically lowers the costin terms of financial resources, human effort, and timeof examining unexplored regions of composition space, including regions that might be avoided as unlikely candidates for an expensinve one-off study. Experience has shown that high-throughput screening can be a useful tool for solving real-world problems in materials discovery if three broad criteria are met: In general, the approach is suitable for a well-defined problem for which samples can be prepared using parallelized synthesis and evaluated using a suitable high-throughput screen. High-throughput techniques are also valuable for investigations of known materials systems, where the goal is to elucidate the composition dependence of materials properties. The codeposited composition spread technique has proven particularly effective for exploring energy-related materials in a wide range of investigations.
(12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27)
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109
Name Cerium(IV) oxidesamarium doped Cerium(IV) oxidegadolinium doped Zirconium(IV) oxide-yttria stabilized
Purity -
Dimensions diam. L 2-3 3-5 mm diam. L 2-3 3-5 mm diam. H 2-3 3-5 mm
Nickel Nickel Copper Copper Copper Copper Zinc Zinc Zirconium Niobium Molybdenum Molybdenum Molybdenum Rhodium Palladium Silver Silver Silver Silver Silver Silver
Ni Ni Cu Cu Cu Cu Zn Zn Zr Nb Mo Mo Mo Rh Pd Ag Ag Ag Ag Ag Ag
99.995% trace metals basis 99.98% trace metals basis 99.999% trace metals basis 99.98% trace metals basis 99.98% trace metals basis 99.98% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.98% trace metals basis 99.8% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.99% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis
thickness 0.25 mm thickness 0.1 mm thickness 1.0 mm thickness 0.25 mm thickness 0.025 mm thickness 0.5 mm thickness 1.0 mm thickness 0.25 mm thickness 0.1 mm thickness 0.25 mm thickness 1.0 mm thickness 0.1 mm thickness 0.025 mm thickness 0.025 mm thickness 1.0 mm thickness 2.0 mm thickness 1.0 mm thickness 0.5 mm thickness 0.25 mm thickness 0.1 mm thickness 0.025 mm
110
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Composition Cd In In
Purity 99.99% trace metals basis 99.999% trace metals basis 99.99% trace metals basis
Prod. No. 265411-11G 326631-2.3G 326631-36.8G 357294-4.6G 357294-18.4G 357294-41.4G 357308-1.8G 357308-7.2G 265756-9G 265756-36G 262897-10.4G 262897-41.6G 357243-8.4G 357243-18.9G 262919-9G 262919-31G 357189-24G 357189-96G 267546-12G 267546-48G 357197-6G 357197-24G 267538-2.4G 267317-3.3G 267317-13.2G 357324-3.5G 349372-14G 267260-7G 267260-14G 349321-3.5G 349321-14G 267252-1.3G 267252-5.3G 267252-5.6G 349356-600MG 349356-2.4G 349364-350MG 349364-1.4G 265829-6G 265829-24G 349240-3G 349240-12G 265810-1.2G 265810-4.8G 349275-600MG 349275-2.4G 268461-300MG 268461-1.2G
Indium Tin Tantalum Tantalum Tantalum Tungsten Tungsten Tungsten Tungsten Rhenium Iridium Platinum Platinum Platinum Platinum
In Sn Ta Ta Ta W W W W Re Ir Pt Pt Pt Pt
99.999% trace metals basis 99.998% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.9% trace metals basis 99.98% trace metals basis 99.9% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.99% trace metals basis
thickness 0.1 mm thickness 0.5 mm thickness 0.25 mm thickness 0.05 mm thickness 0.025 mm thickness 0.5 mm thickness 0.25 mm thickness 0.127 mm thickness 0.05 mm thickness 0.25 mm thickness 0.25 mm thickness 1.0 mm thickness 0.5 mm thickness 0.25 mm thickness 0.1 mm
Pt Pt Au Au Au Au Au
99.99% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.9% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.99% trace metals basis
thickness 0.05 mm thickness 0.025 mm thickness 0.5 mm thickness 0.25 mm thickness 0.1 mm thickness 0.05 mm thickness 0.025 mm
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111
Materials Science
Pt/C Electrocatalysts
Accelerate Your Fuel Cell Research
Aldrich Materials Science offers a selection of new Pt-based catalysts for Proton Exchange Membrane Fuel Cells (PEMFC) and Direct Methanol Fuel Cells (DMFC). Benefits of these materials include: yy Consistent nanoparticle sizes for high surface areas and maximum electrocatalytic activity yy Increased stability and minimal particle growth at elevated temperatures yy Low-sulfur, highly conductive carbon supports to prevent catalyst poisoning Advances in catalyst fabrication, such as the use of optimally sized platinum nanoparticles, enable increased performance of PEMFC and DMFC devices.1 Alloys, such as Pt3Co and Pt-Ru, also offer additional advantages due to their cost efficiency, high activity towards oxygen reduction, and enhanced tolerance to carbon monoxide.2-3
Materia
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s for Solid s in Material Advance Cells Oxide Fuel ganic Metalor ion High Purity for CPV Fabricat rs Precurso s: New x Hydride tors Comple Conduc of Lithium cal E ect ochemi ations Mechan Deform Plastic Severe
A New
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Name Platinum on graphitized carbon, 10 wt. % loading Platinum on graphitized carbon, 20 wt. % loading Platinum on graphitized carbon, 40 wt. % loading Platinum Cobalt on carbon, 30 wt. % Pt3Co loading Platinum-Ruthenium alloy on graphitized carbon, 20 wt. % Pt, 10 wt. % Ru loading
For more information about fuel cell catalysts and membranes, visit our alternative energy portal at Aldrich.com/energy
1. Starz, K.A.; Auer, A.; Lehmann, T.; Zuber, R. J. Power Sources 2000, 86, 237. 2. Steele, B.C.H.; Heinzel, A. Nature 2001, 414, 345. 3. Stamenkovic, V.; Schmidt, T.J.; Ross, P.N.; Markovic, N.M. J. Phys. Chem. B 2002, 106, 11970
Andries Meijerink Condensed Matter and Interfaces, Debye Institute for NanoMaterials Science Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands Email: a.meijerink@uu.nl
Global energy consumption is on the rise and is projected to double by 2050, compared with worldwide energy consumption rates in 2001.1 Sustainable energy production based on the direct conversion of energy radiated from the sun into heat or electricity is expected to gain importance, as it may be the only renewable source capable of generating sufficient energy to meet the long-term worldwide energy demand.1,2 The capacity of photovoltaic cells to convert sunlight into electricity makes them prime candidates for effective large-scale capture and conversion of solar energy, but at present the contribution of photovoltaic energy is limited, due to its relatively high cost per kilowatt-hour. A reduction in price may be achieved by either lowering production costs or increasing conversion efficiency. Crystalline Si (c-Si) solar cells dominate the photovoltaic market and have energy efficiencies around 15 %. In a solar cell, a single electronhole pair is generated in a semiconductor upon absorbing a photon above the energy bandgap. The most significant loss mechanisms are due to relaxation of "hot" charge carriers that are created upon absorption of a high-energy photon and transmission of photons with energies below the bandgap of the semiconductor material.3 The excess energy of high energy photons is rapidly lost as heat by thermalization. In a detailed balance model developed by Shockley and Queisser,4 the theoretical efficiency limit for a single-junction solar cell with Eg equal to 1.1 eV can be determined to be 30%. A promising approach to raise the theoretical efficiency beyond the Shockley-Queisser limit is to adapt the
Introduction
c-Si Absorption
UC Gain
500
1000
1500
2000
2500
Wavelength (nm)
Figure 1. Potential efficiency gain of down- and 2-photon upconversion for a c-Si solar cell. The green part gives the part of the energy from the solar spectrum that can be converted into electrical energy by a c-Si solar cell, assuming no other losses than spectral mismatch losses. The yellow area gives the energy gain that can be obtained with an ideal upconverter, while the red part gives the maximum gain with an ideal downconverter.
The gain that can be achieved by using a perfect upconverter (in yellow) and perfect downconverter (in red) is about 20 % for each process for c-Si solar cells. In this review, the potential of using lanthanides as downconverters and upconverters will be outlined, after a brief introduction to the unique optical properties of lanthanides.
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113
Luminescent Lanthanides
Lanthanides (Ln) are a group of elements that can be found at the bottom of the periodic table. The 4f inner shell of lanthanides is partially filled with electrons. They are mostly stable in the trivalent state, and the Ln3+ ions have the electronic configuration 4 f n 5 s 2 5 p 6 , where n varies from 0 to 14. The partially filled 4f inner shell is responsible for the characteristic optical and magnetic properties of the lanthanides. The number of configurations for n electrons divided over the 14 4f orbitals is large (14/n), and all of the configurations can have different energies. In Figure 2, the energy level diagrams for the trivalent lanthanide ions, from Ce to Yb, are shown.
42 40 38 36 34 32 30 28 26 24 22 20 18 16 14 12 10 8 6 4 2 0
2
Figure 3. (top) Luminescence of blue (Eu2+), green (Tb3+) and red (Eu3+) phosphors for (compact) fluorescent tubes under 254 nm UV irradiation. The white luminescence is obtained for a mixture of the blue, green and red phosphors. (bottom) Euro banknote under 360 nm UV irradiation. The red, green and blue luminescence from the stars and fibers is generated by Eu2+ (blue and green) and Eu3+ (red).
At the top, the emission of light by three lanthanide doped luminescent materials, or "phosphors," for application in fluorescent tubes is shown. At the bottom, the luminescence of a Euro banknote under UV-irradiation is shown as it is observed under the blacklight at a cash register. The red, green, and blue lights originate from Eu3+ and Eu2+ ions. The choice of safeguarding the Euro banknotes with the element europium has been deliberate.7 For up- and downconversion for solar cells, lanthanide ions are ideal candidates. The rich energy level structure allows many pathways to add or split the energy of incoming photons without significant energy losses. The process can take place within a single type of lanthanide ion, or it can involve energy transfer between two or more types of ions codoped within the same host material.
Upconversion
Upconversion with lanthanides was discovered in the early 1960s.5 For the lanthanide ion couple Yb3+-Er3+, it was shown that upon infrared excitation of Yb3+ around 1000 nm, green and red luminescence from Er3+ is observed. The steps involved are illustrated in Figure 4.
F 5/2
3
H4
I 9/2
I4
H5/2
F0
F6
H15/2
I8
4 15 /2
H6
2 7 /2
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
20
Figure 2. Free ion energy levels of the trivalent lanthanide ions from Ce3+ (4f1) to Yb3+ (4f13). Levels are labelled by term symbols or, for some higher levels, capital letters.
1,000 cm-1
4 4
F7/2
The horizontal black lines represent energy levels, labeled by term symbols 2S+1LJ. This diagram, often called the "Dieke diagram,"6 exhibits the rich energy level structure of the free ions. It is also representative of the 4f energy level structure of these ions when doped into crystalline or glassy materials, because the optically-active 4f electrons are shielded from the host environment by the outer filled 5s and 5p orbitals. The shielding also results in sharp, atomic-like lines in the optical spectra. Quantum efficiency, defined as the number of photons emitted divided by the number of photons absorbed, can be very high, typically above 90%. The high efficiencies are the reason for the widespread application of lanthanides in light-emitting devices. In Figure 3, efficient luminescence is demonstrated for two applications.
15
4 4 4
10
F5/2
F7/2
Yb3+
Er3+
I15/2
Figure 4. Schematic energy level scheme for the Yb/Er couple. The Yb3+ ion absorbs around 980 nm and transfers the energy from the 2F5/2 level to the 4I11/2 level of Er3+. Subsequent energy transfer from a second excited Yb3+ ion to Er3+ (4I11/2), excites Er3+ ion to to the 4F7/2 excited state. After multi-phonon relaxation to the lower lying 4S3/2 and 4F9/2 states, green and red emission are observed, as indicated.
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The process was originally called "addition de photons par transfer denergie" (APTE), but it is now generally known as energy transfer upconversion (ETU), and it is the most efficient mechanism for upconversion with lanthanide ions.5 Different types of energy transfer mechanisms are possible, but non-radiative energy transfer via dipoledipole interaction is mainly the dominant mechanism. Efficient energy transfer requires the ions to be in close proximity; thus, ETU requires high concentration of the dopants. One of the most efficient upconverter materials for NIR to VIS upconversion is NaYF4: Er3+, Yb3+. Lanthanide upconverters have been applied in solar cells. Upconversion efficiency is low, and most demonstrations merely serve as proof of the principle showing that an increase in efficiency can be realized by applying an upconversion layer. In general, the upconverter is applied at the back of a cell as an electrically isolated layer. A back reflector reflects all emitted photons back into the solar cell. The first experiment was conducted on GaAs (Aldrich Prod. No. 329010) solar cells combined with a vitroceramic material doped with Yb3+ and Er3+ under extremely high excitation densities. An efficiency of 2.5 % of the solar cell was obtained. In 2005, Shalav et al.8 showed upconversion under lower excitation density of 2.4 W/cm2 reaching 3.4 % quantum efficiency at 1,523 nm in a crystalline silicon solar cell with NaYF4 doped with Er3+ as upconverter. Since c-Si has a rather small bandgap (1.12 eV), transmission losses are not as high as for wider bandgap solar cells. Therefore, the efficiency gain for larger bandgap solar cells can be higher. Presently, upconversion efficiencies are still rather low; only at high excitation densities, exceeding the solar power density, are efficiencies above 1 % reached. Concentration of solar light is needed. In addition, it is crucial to broaden the absorption spectrum, as the absorption lines for lanthanide upconverters are narrow, and absorption strengths are low for the parity forbidden transitions within the 4fn configuration. Broadening of the absorption spectrum for lanthanide upconverters can be achieved by using a sensitizer with a broad absorption band and a narrow emission line resonant with the lanthanide absorption line. Sensitization can be achieved by an external sensitizer (e.g., quantum dots), or an internal sensitizer (e.g., transition metal ions). Even more challenging are options to enhance upconversion efficiencies by manipulating emission and excitation processes through plasmonic coupling.9 The use of plasmonic effects with upconverter materials is a new and emerging field, with many possibilities and challenges.
around 1,000 nm. The absence of other energy levels allows Yb3+ to exclusively "pick up" energy packages of 10,000 cm-1 from other codoped lanthanide ions and emit photons at ~1,000 nm, which can be absorbed by c-Si. Efficient downconversion using Yb3+ via resonant energy transfer requires donor ions with an energy level at about 20,000 cm-1 and an intermediate energy level at approximately 10,000 cm-1. Examination of Figure 2 reveals potential ion couples, such as Er3+ - Yb3+, Nd3+ - Yb3+, Ho3+ - Yb3+, and Pr3+ - Yb3+. As an example, Figure 5 shows the energy transfer processes leading downconversion for the Pr3+-Yb3+ couple.
25
3 3
20
P2 P1, 1I6 P0 D2
15
10
F5/2
G4 F4 F3 H6
F5/2
3 3 3
H5 H4
2
F7/2
Yb3+
Pr3+
Yb3+
F7/2
Figure 5. Energy levels and quantum cutting mechanism for the Pr3+ - Yb3+ couple. A two-step energy transfer occurs upon excitation into the 3PJ (J=0, 1, 2) and 1I6 levels of Pr3+. A single visible photon absorbed by these levels is thereby converted into two ~1,000 nm photons. Solid, dotted, and curved arrows represent optical transitions, nonradiative energy transfer processes, and nonradiative relaxation, respectively.
After excitation into one of the 3PJ levels between 450 and 490 nm, efficient two-step energy transfer to two neighboring Yb3+ ions occurs with internal quantum efficiencies close to 200 %. Both Yb3+ ions can emit a 1,000 nm photon that can be absorbed by a c-Si solar cell. The promising results of downconversion with lanthanides does not mean that one can expect implementation of downconversion materials in solar cells in the near future. On the contrary, serious challenges need to be addressed before downconversion materials can be applied. A major limitation, just as for upconversion, is the weak absorption for 4fn transitions. A solution may be a sensitizer that absorbs efficiently in the UV/VIS and transfers the energy to the downconversion couple. Work on the sensitization is only just starting. A second issue is concentration quenching. High Yb3+-concentrations are needed to achieve complete energy transfer to the Yb3+ acceptor ions. At these high concentrations, quenching of the emission occurs through energy migration over the Yb3+-sublattice (concentration quenching) and lowers efficiency. Finally, if an efficient downconversion couple is developed, the material needs to be incorporated in a transparent layer on top of the solar cell. To prevent losses due to isotropic emission, an anti-reflective coating for the 1,000-nm Yb3+ emission is required on top of the downconversion layer. Clearly, the road toward implementation is long.
Downconversion
The idea to obtain quantum efficiencies above 100 % by creating multiple photons through "cutting" a single photon into two lowerenergy photons was first proposed by Dexter in 1957.10 The mechanism involved the simultaneous energy transfer from a donor to two acceptors, each accepting half the energy of the excited donor. It was not until 1974 that experimental evidence for quantum yields above 100 % was obtained, for YF3:Pr3+.11,12 The mechanism was not the one proposed by Dexter, but it involved two sequential emission steps from the high-energy 1S0. Later, quantum cutting via two sequential energy transfer steps in the Gd3+-Eu3+ couple was discovered and, based on the analogy of the two-step energy transfer process in upconversion, it was called "downconversion."13 The aim in all this work was to achieve the emission of two visible photons from a single UV photon in order to boost the efficiency of light-emitting devices. The potential of downconversion for increasing the efficiency of solar cells was realized soon afterwards.2 The first experimental demonstration of downconversion for solar cells involved the Tb3+-Yb3+ couple, where quantum cutting was achieved through cooperative energy transfer from Tb3+ to two Yb3+ ions, the very mechanism suggested almost 50 years earlier by Dexter.15 It is evident from the Dieke diagram (Figure 2) that the energy level structure of Yb3+ is ideally suited for use in downconversion for c-Si solar cells. The Yb3+ ion has a single excited state approximately 10,000 cm-1 above the ground state, corresponding to an emission of
Conclusions
Spectral conversion for solar cells is an emerging concept in the field of photovoltaics, and it has the potential to increase significantly the efficiency of solar cells. Lanthanide ions are ideal candidates for spectral conversion, due to their high luminescence efficiencies and rich energy level structure that allows for great flexibility in the upconversion and downconversion of photons in a wide spectral region (NIR-VIS-UV). Proof-of-concept experiments have been reported for upconversion, demonstrating an increase in efficiency for sub-bandgap illumination for different types of solar cells by application of upconverter materials. The challenges lie in improving upconversion efficiency, especially for the relatively low excitation densities that are typical for solar illumination.
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115
Quantum cutting through downconversion has only been studied in the last decade. It offers great potential for efficiency enhancement for narrow bandgap solar cells, such as c-Si solar cells. Efficient downconversion has been reported for several lanthanide couples. In these couples, Yb3+ serves as an ideal acceptor with a single excited state, just above the bandgap of c-Si. High internal quantum yields (close to 200 %) have been demonstrated and are independent of the incident power. Before implementation in solar cell systems can be realized, some serious issues need to be addressed: sensitization, concentration quenching, and a transparent downconversion layer on top of the solar cell. Research on solving the various issues is in progress, and new results can be expected in the coming years. Based on these results, it will become clear if photon management using lanthanides is indeed a viable option to realize more efficient solar cells.
References
(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) Lewis, N. S.; Nocera, D. G. PNAS 2006, 103, 15729. Morton, O. Nature 2006, 443, 19. Richards, B. S. Sol. Energy Mater. Sol. Cells 2006, 90, 2329. Shockley, W.; Queisser, H. J. J. Appl. Phys. 1961, 32, 510. Auzel, F. Chem. Rev. 2004, 104, 139. Dieke, G. H.; Crosswhite, H. M. Applied Optics 1963, 2, 675. Suyver, F.; Meijerink, A. Chemisch2Weekblad 2002, 4, 12. Shalav, A.; Richards, B. S.; Trupke, T.; Kramer, K. W.; Gudel, H. U. Appl. Phys. Lett. 2005, 86, 013505. Baluschev, S.; Yu, F.; Miteva, T.; Ahl, S.; Yasuda, A.; Nelles, G.; Knoll, W.; Wegner, G. Nano Lett. 2005, 12, 2482. Dexter, D. L. Phys. Rev. 1957, 108, 630. Sommerdijk, J. L.; Bril, A.; de Jager, A. W. J. Lumin. 1974, 8, 341. Piper, W. W.; DeLuca, J. A.; Ham, F. S. J. Lumin. 1974, 8, 344. Wegh, R. T.; Donker, H.; Oskam, K. D.; Meijerink, A. Science 1999, 283, 663. Trupke, T.; Green, M. A.; Wrfel, P. J. Appl. Phys. 2002, 92, 1668. Vergeer, P.; Vlugt, T. J. H.; Kox, M. H. F.; den Hertog, M. I.; van der Eerden, J. P. J. M.; Meijerink, A. Phys. Rev. B 2005, 71, 014119. van der Ende, B. M.; Aarts, L.; Meijerink, A. Phys. Chem. Chem. Phys. 2009, 11, 11081.
MgO MgO
powder powder
99.999% 97%
Aluminum isopropoxide
Al[OCH(CH3)2]3
Aluminum hydroxide hydrate Silicon aluminum oxynitride Calcium nitride Calcium sulfide Calcium fluoride Calcium fluoride Gallium nitride Strontium Strontium fluoride Strontium fluoride Yttrium(III) oxide Yttrium(III) oxide
Al(OH)3 xH2O SiAl6N6O2 Ca3N2 CaS CaF2 CaF2 GaN Sr SrF2 SrF2 Y2O3 Y2O3
95% 99.9% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99% 99.995% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.99% trace metals basis
powder powder powder random crystals powder powder random pieces solid powder powder powder
Yttrium(III) fluoride Yttrium(III) chloride Yttrium(III) tris(isopropoxide) Yttrium aluminum oxide Barium carbonate Barium fluoride
99.99% trace metals basis 99.99% trace metals basis 99% trace metals basis 99.999% trace metals basis 98%
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Form solid
La(NO3)3 6H2O
solid
LaPO4 xH2O
chunks
587176-25G
Europium(III) oxide Europium(III) oxide Gadolinium(III) chloride Gadolinium(III) nitrate hexahydrate Gadolinium(III) nitrate hexahydrate Terbium(III) nitrate hexahydrate Terbium(III) nitrate pentahydrate Terbium(III) oxide Terbium(III,IV) oxide Thulium(III) nitrate pentahydrate Ytterbium(III) nitrate pentahydrate Ytterbium(III) nitrate pentahydrate
Eu2O3 Eu2O3 GdCl3 Gd(NO3)3 6H2O Gd(NO3)3 6H2O Tb(NO3)3 6H2O Tb(NO3)3 5H2O Tb2O3 Tb4O7 Tm(NO3)3 5H2O Yb(NO3)3 5H2O Yb(NO3)3 5H2O
99.999% trace metals basis 99.99% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.9% trace metals basis 99.99% trace metals basis 99.999% trace metals basis 99.9% 99.999% 99.9% trace metals basis
powder and chunks powder beads crystals and lumps solid crystals and lumps solid powder powder powder chunks crystals and lumps
Sulfur Copper Copper Copper Copper Copper Copper(II) chloride Copper(I) chloride Copper(I) chloride
99.99% trace metals basis 99.9999% trace metals basis 99.9998% trace metals basis 99.9995% trace metals basis 99.999% trace metals basis 99.999% trace metals basis 99.995% trace metals basis 99.99% trace metals basis 99.995% trace metals basis
flakes rod, diam. 11 mm rod, diam. 19 mm beads platelets, thickness 6.3 mm powder powder beads powder
For questions, product data, or new product suggestions, contact Aldrich Materials Science at matsci@sial.com.
117
Purity 99.999% trace metals basis 99.999% trace metals basis 99.9995% trace metals basis
Prod. No. 203149-10G 203149-50G 517453-5G 517453-25G 203319-1G 203319-5G 203319-25G 263273-10G 263273-50G 413089-1G 413089-5G 427128-5G 427128-25G 427128-100G 450898-5G 450898-25G 450898-50G 329010-1G 209643-50G 209643-250G 204307-5G 204307-20G 204307-100G 229865-5G 229865-20G 229865-100G 264113-5G 264113-25G 203424-5G 203424-25G 289418-10G 289418-50G 449210-2G 449210-10G 548456-1G 548456-10G 429414-5G 429414-25G 203440-1G 203440-10G 203440-50G 403318-5G 740942-5G
Ga Ga2Cl4 GaCl3
99.999% trace metals basis 99.999% trace metals basis 99.999% trace metals basis
crystalline beads
Gallium(III) chloride
GaCl3
beads
GaAs Se Se
99.999% trace metals basis 99.99% trace metals basis 99.999% trace metals basis
Selenium
Se
powder
Indium Indium(III) oxide Indium(III) oxide Indium(I) chloride Indium(II) chloride Indium(III) chloride Indium(III) chloride
99.999% trace metals basis 99.999% trace metals basis 99.99% trace metals basis 99.999% 99.9% 99.999% trace metals basis 99.999% trace metals basis
beads, diam. 2-5 mm powder powder powder powder powder powder and chunks
In2Se3 InSb
lumps -
Quantum Dots
For a complete list of available materials, visit Aldrich.com/quantumdots
Name Lumidot CdS, 380, core-type quantum dots, 5 mg/mL in toluene,380 core-type quantum dots Lumidot CdS, 400, core-type quantum dots, 5 mg/mL in toluene, 400 core-type quantum dots Lumidot CdS, 420, core-type quantum dots, 5 mg/mL in toluene, 420 core-type quantum dots Lumidot CdS, 440, core-type quantum dots, 5 mg/mL in toluene, 440 core-type quantum dots Lumidot CdS, 460, core-type quantum dots, 5 mg/mL in toluene, 460 core-type quantum dots Lumidot CdS, 480, core-type quantum dots, 5 mg/mL in toluene, 480 core-type quantum dots Lumidot CdSe, 480, core-type quantum dots, 5 mg/mL in toluene, 480 core-type quantum dots Lumidot CdSe, 520, core-type quantum dots, 5 mg/mL in toluene, 520 core-type quantum dots Lumidot CdSe, 560, core-type quantum dots, 5 mg/mL in toluene, 560 core-type quantum dots Lumidot CdSe, 590, core-type quantum dots, 5 mg/mL in toluene, 590 core-type quantum dots Lumidot CdSe, 610, core-type quantum dots, 5 mg/mL in toluene, 610 core-type quantum dots Lumidot CdSe, 640, core-type quantum dots, 5 mg/mL in toluene, 640 core-type quantum dots Particle Size (nm), abs (nm) ~2.3, 350370 ~2.9, 370390 ~3.4, 390410 ~4.2, 410430 ~5.0, 430450 ~5.6, 450470 ~2.1, 455465 ~2.5, 495505 ~3.3, 535545 4.0-4.3, 565575 ~5.0, 585595 ~6.6, 615625 Fluorescence Emission (nm) em = 370390 em = 390410 em = 410430 em = 430450 em = 450470 em = 470490 em = 475485 em = 515525 em = 555565 em = 585595 em = 605615 em = 635645 Prod. No. 662429-10ML 662410-10ML 662402-10ML 662380-10ML 662372-10ML 662364-10ML 662356-10ML 662437-10ML 662445-10ML 662607-10ML 662488-10ML 662461-10ML
118
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Materials Science
O OH
H2N HO O O OH NH2 NC O OH O OH
HO O
O OH
O OH
H2ADC Prod. No. 724440
O HO HO O
O OH OH O HO O OH O R
R R= R
OH O HO O
N N N
HO O OH O HO O OH O
Contact us at matsci@sial.com to discuss materials for your own MOF. For more information, visit Aldrich.com/renewable
Basolite is a registered trademark of BASF SE.
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